CN102127583A - Method for preparing anti-para amino adamantanol - Google Patents
Method for preparing anti-para amino adamantanol Download PDFInfo
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- CN102127583A CN102127583A CN2010100229703A CN201010022970A CN102127583A CN 102127583 A CN102127583 A CN 102127583A CN 2010100229703 A CN2010100229703 A CN 2010100229703A CN 201010022970 A CN201010022970 A CN 201010022970A CN 102127583 A CN102127583 A CN 102127583A
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- aminoadamantan
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- aminoadamantan alcohol
- pig kidney
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Abstract
The invention relates to a method for preparing anti-para amino adamantanol. The method comprises the following steps of: (1) preparing a crude anti-para amino adamantanol product; (2) extracting pig kidney amino-acylase; and (3) resolving amino adamantanol so as to obtain the anti-para amino adamantanol with higher purity. Compared with the prior art, the method has the advantages that: racemic para amino adamantanol is successfully dissolved by using the pig kidney amino-acylase for the first time, so that the anti-para amino adamantanol is obtained; the method has a simple process and a high conversion rate; and the maximum yield can reach 71.8 percent.
Description
Technical field
The present invention relates to a kind of preparation method of pharmaceutical intermediate, especially relate to a kind of trans preparation method aminoadamantan alcohol.
Background technology
Trans is the intermediate of synthetic anti-AIDS medicine to aminoadamantan alcohol, and the synthetic route of having reported is to separate along opposing the kharophen adamantanol with crystallization process or post partition method, and the total reaction yield is 27%.
The trans preparation hydrolysis 42 different third imino-adamantanols to aminoadamantan alcohol prepare and trans aminoadamantan alcohol have been taken some twists and turns in the selection of hydrolytic reagent, mainly selected for use some acid reagents to make hydrolytic reagent, experimental results show that effect is bad, as boric acid, acid diatomite, hydrochloric acid, sulfuric acid, percent hydrolysis from 10% to 30% does not wait.The back adopts sodium hydroxide hydrolysis can obtain experimental result preferably, and percent hydrolysis is 98%-99%, and the mother liquor of hydrolysis can be applied mechanically 3-4 time adding under the situation of appropriate bases, does not influence the purity of product.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of yield higher trans preparation method to aminoadamantan alcohol for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
(1) trans preparation: will be dissolved in the Glacial acetic acid to aminoadamantan alcohol to aminoadamantan alcohol crude product, be warming up to 60-65 ℃ to aminoadamantan alcohol is dissolved fully, after the clarification of question response system, utilize constant pressure funnel at the uniform velocity to drip diacetyl oxide, continue to be warming up to 75-80 ℃, isothermal reaction 2-3h, the gained reaction solution is carried out underpressure distillation, remove Glacial acetic acid and excessive acetic anhydride via, the adding distil water washing is 4-5 time again, drains then to a large amount of white powdery solids occurring, add acetone again, the dissolving postcooling crystallization that refluxes obtains filter cake, and filter cake is carried out suction filtration and adopts washing with acetone, the filter cake oven dry is promptly obtained trans to aminoadamantan alcohol crude product again;
(2) extraction of pig kidney L-Aminoacylase: the pig kidney of getting the fresh matter of emedullating, clean the back section, the shop dish also drains, place the interior freezing 1h of-10 ℃ of refrigerated tanks to thaw again, add the Diluted Alcohol aqueous solution and cobalt chloride, in tissue mashing machine, smash into homogenate and utilize ultrasonication 10-15min, the homogenate that obtains places whizzer, the control rotating speed is the centrifugal 20min of 3000-4000rpm, get supernatant liquid, the ethanol and the ammonium sulfate that add 95wt% staticly settle, and placing whizzer inner control rotating speed again is the centrifugal 20min of 3000-4000rpm, obtain gray precipitate, in precipitation, add acetone and dewater, obtain the beige powdery granule behind the suction filtration, be pig kidney L-Aminoacylase;
(3) to the fractionation of amino Buddha's warrior attendant alcohol: with trans aminoadamantan alcohol being dissolved in the distilled water that step (1) obtains; utilize NaOH solution to regulate pH value to 6.7; be warming up to 30-35 ℃; add the pig kidney L-Aminoacylase that step (2) makes; isothermal reaction 24h; carry out suction filtration after reaction finishes and utilize hydrochloric acid to regulate pH value of filtrate to 5.6; naturally cooling after being warming up to 100 ℃; suction filtration is removed the white floss of generation and filtrate is concentrated into original volume 1/3 and obtains secondary filtrate; secondary filtrate is concentrated into 1/20 of secondary filtrate volume after the Zeo-karb separation and purification; utilize salt acid for adjusting pH value to 5.56; control reaction temperature is 5 ℃; crystallization; in 60 ℃ of oven dry, the white solid that obtains utilizes the aqueous ethanolic solution recrystallization of 50wt% behind the suction filtration, promptly gets trans to aminoadamantan alcohol.
The weight ratio to aminoadamantan alcohol and Glacial acetic acid in the described step (1) is 1: (5-5.5), the volume ratio of described Glacial acetic acid, diacetyl oxide and acetone is 2: (0.6-0.7): 1.
The weight ratio of the pig kidney in the described step (2), the Diluted Alcohol aqueous solution and cobalt chloride is 1: 1.5: (0.03-0.05).
The Diluted Alcohol aqueous solution in the described step (2) is the aqueous ethanolic solution of 30wt%.
Supernatant liquid in the described step (2) and the alcoholic acid volume ratio of 95wt% are 1: 2, and the ethanol of described 95wt% and the weight ratio of ammonium sulfate are (550-560): 1, and the weight ratio of described gray precipitate and acetone is 1: (3.5-4).
Trans weight ratio to aminoadamantan alcohol, distilled water and pig kidney L-Aminoacylase in the described step (3) is 1: (65-70): 0.1.
The concentration of NaOH solution is 2mol/L in the described step (3), and the concentration of described hydrochloric acid is 2mol/L.
Zeo-karb in the described step (3) is No. 732 storng-acid cation exchange resins.
Compared with prior art, the present invention first with pig kidney L-Aminoacylase successfully split DL to aminoadamantan alcohol, obtain transly to aminoadamantan alcohol, this procedure is simple, transformation efficiency is also higher.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of trans preparation method to aminoadamantan alcohol, this method may further comprise the steps:
(1) trans preparation: 41.2g is dissolved in the 200ml Glacial acetic acid aminoadamantan alcohol to aminoadamantan alcohol crude product, be warming up to 65 ℃ to aminoadamantan alcohol is dissolved fully, after the clarification of question response system, utilize constant pressure funnel at the uniform velocity to drip 66.6ml (about 0.7mol) diacetyl oxide, continue to be warming up to 80 ℃, isothermal reaction 2h, the gained reaction solution is carried out underpressure distillation, remove Glacial acetic acid and excessive acetic anhydride via, adding distil water is 5 times again, each 10mL, drain then to a large amount of white powdery solids occurring, add 100ml acetone again, the dissolving postcooling crystallization that refluxes obtains filter cake, filter cake is carried out suction filtration and adopts the small amount of acetone washing, with after the filtrate decompression distillation, repeat above operation steps twice, gained solid oven dry back mix promptly obtain trans to aminoadamantan alcohol crude product, product weight 47.2g, yield are 81.3%;
(2) extraction of pig kidney L-Aminoacylase: the pig kidney of getting the fresh matter of emedullating; cleaning back section, shop dish and drench does; nearly weigh 200g, place the interior freezing 1h of-10 ℃ of refrigerated tanks to thaw again, the 30wt% Diluted Alcohol aqueous solution and the 8g cobalt chloride that add 1.5 times of pig kidney weights (studies have shown that Co
2+Be the active ions of acylase), in tissue mashing machine, smash into homogenate and utilize ultrasonication 10min, the homogenate that obtains places whizzer, the control rotating speed is the centrifugal 20min of 3500rpm, get supernatant liquid, adding 2 times of ethanol and 1g ammonium sulfate to the 95wt% of supernatant liquid volume staticly settles, placing whizzer inner control rotating speed again is the centrifugal 20min of 3500rpm, obtain gray precipitate, adding 100ml acetone in precipitation dewaters, obtain 20g beige powdery granule behind the suction filtration, be pig kidney L-Aminoacylase, place under-10 ℃ of conditions preserve standby;
(3) to the fractionation of amino Buddha's warrior attendant alcohol: take by weighing trans that step (1) obtains aminoadamantan alcohol 4.35g is dissolved in the 300ml distilled water; utilize concentration to regulate pH value to 6.7 for the NaOH solution of 2mol/L; be warming up to 35 ℃; add the pig kidney L-Aminoacylase 0.435g that step (2) makes; isothermal reaction 24h; carry out suction filtration after reaction finishes and utilize concentration to regulate pH value of filtrate to 5.6 for the hydrochloric acid of 2mol/L; naturally cooling after being warming up to 100 ℃; suction filtration is removed the white floss of generation and filtrate is concentrated into 100ml; again through No. 732 storng-acid cation exchange resin separation and purification; collection is concentrated into 5ml after containing trans solution to aminoadamantan alcohol (triketohydrindene hydrate detection); utilize the salt acid for adjusting pH value to 5.56 of concentration for 2mol/L; control reaction temperature is 5 ℃; crystallization; behind the suction filtration in 60 ℃ of oven dry; the white solid that obtains utilizes the aqueous ethanolic solution recrystallization of 50wt%; it is trans to aminoadamantan alcohol promptly to get the 1.11g product; optically-active=+ 17.58 ° (HCl of C=2.5mol/L) (standard value: [α] 25D=+17.6 °), yield reaches 71.8%.
Embodiment 2
A kind of trans preparation method to aminoadamantan alcohol, this method may further comprise the steps:
(1) trans preparation: 40g is dissolved in the 200g Glacial acetic acid (190ml) aminoadamantan alcohol to aminoadamantan alcohol crude product, be warming up to 60 ℃ to aminoadamantan alcohol is dissolved fully, after the clarification of question response system, utilize at the uniform velocity Dropwise 5 7ml diacetyl oxide of constant pressure funnel, continue to be warming up to 75 ℃, isothermal reaction 2h, the gained reaction solution is carried out underpressure distillation, remove Glacial acetic acid and excessive acetic anhydride via, adding distil water is 4 times again, each 10mL, drain then to a large amount of white powdery solids occurring, add 95ml acetone again, the dissolving postcooling crystallization that refluxes obtains filter cake, filter cake is carried out suction filtration and adopts small amount of acetone to wash, again the filter cake oven dry is promptly obtained trans aminoadamantan alcohol crude product;
(2) extraction of pig kidney L-Aminoacylase: the pig kidney of getting the fresh matter of emedullating, clean the back section, shop dish and drench are done, weight is 100g, place the interior freezing 1h of-10 ℃ of refrigerated tanks to thaw again, the Diluted Alcohol aqueous solution 150g and the cobalt chloride 3g that add 30wt%, in tissue mashing machine, smash into homogenate and utilize ultrasonication 15min, the homogenate that obtains places whizzer, the control rotating speed is the centrifugal 20min of 3000rpm, get supernatant liquid 100ml, the ethanol 200ml and the 0.29g ammonium sulfate that add 95wt% staticly settle, placing whizzer inner control rotating speed again is the centrifugal 20min of 3000rpm, obtains the 5.7g gray precipitate, adds 25ml acetone and dewater in precipitation, obtain the beige powdery granule behind the suction filtration, be pig kidney L-Aminoacylase;
(3) to the fractionation of amino Buddha's warrior attendant alcohol: take by weighing trans that step (1) obtains aminoadamantan alcohol 3g is dissolved in the 195ml distilled water; utilize concentration to regulate pH value to 6.7 for the NaOH solution of 2mol/L; be warming up to 30 ℃; add the pig kidney L-Aminoacylase 0.3g that step (2) makes; isothermal reaction 24h; carry out suction filtration after reaction finishes and utilize concentration to regulate pH value of filtrate to 5.6 for the hydrochloric acid of 2mol/L; naturally cooling after being warming up to 100 ℃; suction filtration is removed the white floss of generation and filtrate is concentrated into 65ml; after No. 732 storng-acid cation exchange resin separation and purification, be concentrated into 3.25ml again; utilize the salt acid for adjusting pH value to 5.56 of concentration for 2mol/L; control reaction temperature is 5 ℃; crystallization; behind the suction filtration in 60 ℃ of oven dry; the white solid that obtains utilizes the aqueous ethanolic solution recrystallization of 50wt%, and it is trans to aminoadamantan alcohol promptly to get product.
Embodiment 3
A kind of trans preparation method to aminoadamantan alcohol, this method may further comprise the steps:
(1) trans preparation: 40g is dissolved in the 220g Glacial acetic acid (210ml) aminoadamantan alcohol to aminoadamantan alcohol crude product, be warming up to 65 ℃ to aminoadamantan alcohol is dissolved fully, after the clarification of question response system, utilize constant pressure funnel at the uniform velocity to drip the 74ml diacetyl oxide, continue to be warming up to 80 ℃, isothermal reaction 3h, the gained reaction solution is carried out underpressure distillation, remove Glacial acetic acid and excessive acetic anhydride via, adding distil water is 5 times again, each 10mL, drain then to a large amount of white powdery solids occurring, add 105ml acetone again, the dissolving postcooling crystallization that refluxes obtains filter cake, filter cake is carried out suction filtration and adopts small amount of acetone to wash, again the filter cake oven dry is promptly obtained trans aminoadamantan alcohol crude product;
(2) extraction of pig kidney L-Aminoacylase: the pig kidney of getting the fresh matter of emedullating, clean the back section, shop dish and drench are done, weight is 100g, place the interior freezing 1h of-10 ℃ of refrigerated tanks to thaw again, the Diluted Alcohol aqueous solution 150g and the cobalt chloride 5g that add 30wt%, in tissue mashing machine, smash into homogenate and utilize ultrasonication 15min, the homogenate that obtains places whizzer, the control rotating speed is the centrifugal 20min of 4000rpm, get supernatant liquid 100ml, the ethanol 200ml and the 0.3g ammonium sulfate that add 95wt% staticly settle, placing whizzer inner control rotating speed again is the centrifugal 20min of 4000rpm, obtains the 6.2g gray precipitate, adds 31.5ml acetone and dewater in precipitation, obtain the beige powdery granule behind the suction filtration, be pig kidney L-Aminoacylase;
(3) to the fractionation of amino Buddha's warrior attendant alcohol: take by weighing trans that step (1) obtains aminoadamantan alcohol 3g is dissolved in the 210ml distilled water; utilize concentration to regulate pH value to 6.7 for the NaOH solution of 2mol/L; be warming up to 35 ℃; add the pig kidney L-Aminoacylase 0.3g that step (2) makes; isothermal reaction 24h; carry out suction filtration after reaction finishes and utilize concentration to regulate pH value of filtrate to 5.6 for the hydrochloric acid of 2mol/L; naturally cooling after being warming up to 100 ℃; suction filtration is removed the white floss of generation and filtrate is concentrated into 70ml; after No. 732 storng-acid cation exchange resin separation and purification, be concentrated into 3.5ml again; utilize the salt acid for adjusting pH value to 5.56 of concentration for 2mol/L; control reaction temperature is 5 ℃; crystallization; behind the suction filtration in 60 ℃ of oven dry; the white solid that obtains utilizes the aqueous ethanolic solution recrystallization of 50wt%, and it is trans to aminoadamantan alcohol promptly to get product.
Claims (8)
1. trans preparation method to aminoadamantan alcohol is characterized in that this method may further comprise the steps:
(1) trans preparation: will be dissolved in the Glacial acetic acid to aminoadamantan alcohol to aminoadamantan alcohol crude product, be warming up to 60-65 ℃ to aminoadamantan alcohol is dissolved fully, after the clarification of question response system, utilize constant pressure funnel at the uniform velocity to drip diacetyl oxide, continue to be warming up to 75-80 ℃, isothermal reaction 2-3h, the gained reaction solution is carried out underpressure distillation, remove Glacial acetic acid and excessive acetic anhydride via, the adding distil water washing is 4-5 time again, drains then to a large amount of white powdery solids occurring, add acetone again, the dissolving postcooling crystallization that refluxes obtains filter cake, and filter cake is carried out suction filtration and adopts washing with acetone, the filter cake oven dry is promptly obtained trans to aminoadamantan alcohol crude product again;
(2) extraction of pig kidney L-Aminoacylase: the pig kidney of getting the fresh matter of emedullating, clean the back section, the shop dish also drains, place the interior freezing 1h of-10 ℃ of refrigerated tanks to thaw again, add the Diluted Alcohol aqueous solution and cobalt chloride, in tissue mashing machine, smash into homogenate and utilize ultrasonication 10-15min, the homogenate that obtains places whizzer, the control rotating speed is the centrifugal 20min of 3000-4000rpm, get supernatant liquid, the ethanol and the ammonium sulfate that add 95wt% staticly settle, and placing whizzer inner control rotating speed again is the centrifugal 20min of 3000-4000rpm, obtain gray precipitate, in precipitation, add acetone and dewater, obtain the beige powdery granule behind the suction filtration, be pig kidney L-Aminoacylase;
(3) to the fractionation of amino Buddha's warrior attendant alcohol: with trans aminoadamantan alcohol being dissolved in the distilled water that step (1) obtains; utilize NaOH solution to regulate pH value to 6.7; be warming up to 30-35 ℃; add the pig kidney L-Aminoacylase that step (2) makes; isothermal reaction 24h; carry out suction filtration after reaction finishes and utilize hydrochloric acid to regulate pH value of filtrate to 5.6; naturally cooling after being warming up to 100 ℃; suction filtration is removed the white floss of generation and filtrate is concentrated into original volume 1/3 and obtains secondary filtrate; secondary filtrate is concentrated into 1/20 of secondary filtrate volume after the Zeo-karb separation and purification; utilize salt acid for adjusting pH value to 5.56; control reaction temperature is 5 ℃; crystallization; in 60 ℃ of oven dry, the white solid that obtains utilizes the aqueous ethanolic solution recrystallization of 50wt% behind the suction filtration, promptly gets trans to aminoadamantan alcohol.
2. a kind of trans preparation method according to claim 1 to aminoadamantan alcohol, it is characterized in that, the weight ratio to aminoadamantan alcohol and Glacial acetic acid in the described step (1) is 1: (5-5.5), the volume ratio of described Glacial acetic acid, diacetyl oxide and acetone is 2: (0.6-0.7): 1.
3. a kind of trans preparation method to aminoadamantan alcohol according to claim 1 is characterized in that the weight ratio of the pig kidney in the described step (2), the Diluted Alcohol aqueous solution and cobalt chloride is 1: 1.5: (0.03-0.05).
4. a kind of trans preparation method to aminoadamantan alcohol according to claim 1 is characterized in that the Diluted Alcohol aqueous solution in the described step (2) is the aqueous ethanolic solution of 30wt%.
5. a kind of trans preparation method according to claim 1 to aminoadamantan alcohol, it is characterized in that, supernatant liquid in the described step (2) and the alcoholic acid volume ratio of 95wt% are 1: 2, the ethanol of described 95wt% and the weight ratio of ammonium sulfate are (550-560): 1, and the weight ratio of described gray precipitate and acetone is 1: (3.5-4).
6. a kind of trans preparation method to aminoadamantan alcohol according to claim 1 is characterized in that, the trans weight ratio to aminoadamantan alcohol, distilled water and pig kidney L-Aminoacylase in the described step (3) is 1: (65-70): 0.1.
7. a kind of trans preparation method to aminoadamantan alcohol according to claim 1 is characterized in that, the concentration of NaOH solution is 2mol/L in the described step (3), and the concentration of described hydrochloric acid is 2mol/L.
8. a kind of trans preparation method to aminoadamantan alcohol according to claim 1 is characterized in that the Zeo-karb in the described step (3) is No. 732 storng-acid cation exchange resins.
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| CN2010100229703A CN102127583A (en) | 2010-01-19 | 2010-01-19 | Method for preparing anti-para amino adamantanol |
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| CN2010100229703A CN102127583A (en) | 2010-01-19 | 2010-01-19 | Method for preparing anti-para amino adamantanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110859890A (en) * | 2019-12-06 | 2020-03-06 | 湖北威仕生物药业股份有限公司 | Eucommia ulmoides waist tonifying mixture and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196392A (en) * | 1998-04-27 | 1998-10-21 | 湖北省八峰药化股份有限公司 | Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase |
| US20070225280A1 (en) * | 2006-03-22 | 2007-09-27 | Kevin William Anderson | Adamantyl-pyrazole carboxamides as inhibitors of 11B-hydroxysteroid dehydrogenase |
| CN101492348A (en) * | 2009-02-26 | 2009-07-29 | 泸州万联化工有限公司 | Method for producing 1-adamantane ethanol |
-
2010
- 2010-01-19 CN CN2010100229703A patent/CN102127583A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196392A (en) * | 1998-04-27 | 1998-10-21 | 湖北省八峰药化股份有限公司 | Method for preparing levomethionine by decomposing mixed methionine with amino-acylation-hoydrolase |
| US20070225280A1 (en) * | 2006-03-22 | 2007-09-27 | Kevin William Anderson | Adamantyl-pyrazole carboxamides as inhibitors of 11B-hydroxysteroid dehydrogenase |
| CN101492348A (en) * | 2009-02-26 | 2009-07-29 | 泸州万联化工有限公司 | Method for producing 1-adamantane ethanol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110859890A (en) * | 2019-12-06 | 2020-03-06 | 湖北威仕生物药业股份有限公司 | Eucommia ulmoides waist tonifying mixture and application thereof |
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